Bactericide surfactant compositions

ABSTRACT

A detergent comprising: a) 0.001% to 40% w/v of a bactericidally active water-insoluble cationic compound in its salt form wherein the counterion anion has at least one of the following properties: 1) can generate a water-insoluble salt form, by water-insoluble we mean that less than 10% w/v dissolves in deionised water at 20° C., preferably less than 1% w/v; 2) has a MW of less than 300, (preferably less than 200) but greater than 50 (preferably greater than 75), 3) the dissociation constant (Kd) of the salt is less than 10 −3 , preferably less than 10 −6 ; b) 0.001 to 40% w/v of an anionic surfactant; and c) up to 98% w/v of water.

The invention relates to anionic surfactant compositions containing abactericide, which is a cationic compound, being specifically developedfor fabric cleaning products.

In general, cationic bactericide compounds have low compatibility withanionic based surfactant compositions and they may have a negativeeffect in terms of the cleaning performance of the composition.

Certain cationic compounds, as described below, are well known activesable to provide good disinfecting efficacy both versus gram negative andgram positive bacteria, but have in general low compatible with anionicsurfactants or anionic species in general. Cationic compounds tend toprecipitate with anionic compounds or lose their bactericide efficacydue to the formation of an anionic-cationic complex that doesn't allowthe cationic part of the complex to be available to kill bacteria. Thecationic compounds are, in addition, well known to cause stickiness tofabric surfaces, especially carpet, and are very deleterious for soilre-deposition, which is considered an important factor for fabric care.Generally cationic compounds are metal corrosives making their use inaerosols problematical.

Phenols and phenol based bactericides are other ingredients used inseveral application areas. More and more concerns about theirtoxicological impact is growing, they are considered as potentialcarcinogens and they are generally avoided for this reason.

Aldehydes such as formaldehyde and glutaraldehyde are cheap andbroad-spectrum bactericides, but as with phenols, they are carcinogensor potential carcinogens and also show a tendency to sensitise peoplewho are frequently exposed to them.

The halogens have a long history as bactericide agents. Chloride is theactive atom in household bleach and chloride and bromine are used forwater disinfection. Iodine is very commonly incorporated intoantiseptics, for disinfecting skin and wound dressings, and it is addedto water for water treatment. Iodine used as such or in combination withorganic carrier molecules, iodophors, is used as a liquid disinfectant,but it tends to stains the treated surface with reddish-brown colour.Chlorine is cheap and very effective, but it tends to corrode metalsurface and to decolourise dyes from the fabric surface.

Organic acids are known in the art to be bactericides, examples arecitric acid and salicylic acid. The organic acids are efficient at lowpH, below 5 and more preferably below 4. At these low pH conditions thecleaning performances of the surfactants are reduced and thecompositions work mainly as a bactericide not as a good cleaningproduct.

Alcohols, such as iso-propanol and ethanol, have been used for a longtime in ready to use disinfectants for medical and consumer products. Tobe effective they need to make up a significant percentage of thecomposition, usually 15-70% w/v, the disadvantages are that, being asolvent, they attack many polymers and plastics and cause thecomposition to be high flammable.

Other known ingredients are the essential oils, such as tea tree oil,thyme oil and citronella oil. These products show a low/medium bacteriaefficacy, unless used at high concentration, but at high concentrationsthey may become sensitisers.

In the present invention we have surprisingly found that certaincationic compounds, as described below, are compatible with anionicsurfactants and anionic based products and maintain their bactericidalactivity, having a low toxicological impact and low or no negativeeffects on the composition in terms of cleaning, soil re-deposition andfibre damage.

Whilst not wishing to be bound by theory we believe that “large”counterion anions sterically hinder complex formulation with otheranionic species in the composition.

The cationic compounds of the invention are those that provide agermicidal effect to the concentrate compositions, and especiallypreferred are quaternary ammonium salts which may be characterised bythe general structural formula:

wherein R1, R2, R3 and R4 are independently selected from alkyl, aryl oralkylaryl substituent of from 1 to 26 carbon atoms, and the entirecation portion of the molecule has a molecular weight of at least 165.The alkyl substituents may be long-chain alkyl, long-chain alkoxyaryl,long-chain alkylaryl, halogen-substituted long-chain alkylaryl,long-chain alkylphenoxyalkyl and arylalkyl. The remaining substituentson the nitrogen atoms other than the above mentioned alkyl substituentsare hydrocarbons usually containing no more than 12 carbon atoms. Thesubstituents R1, R2, R3 and R4 may be straight-chained or may bebranched, but are preferably straight-chained, and may include one ormore amide, ether or ester linkages.

Preferred cationic compounds of the invention which are useful in thepractice of the present invention include those which have thestructural formula:

wherein R2 and R3 are each independently the same or different C₈-C₁₂alkyl; or R2 is selected from C12-16 alkyl, C8-18 alkylethoxy or C8-18alkylphenoxyethoxy and R3 is benzyl. Counterion X⁻ is a salt forminganion as described below. The alkyl groups recited in R2 and R3 may bestraight-chained or branched, but are preferably substantially linear.Such useful quaternary compounds are available and include ONYXIDE™ 3300is described as n-alkyl dimethyl benzyl ammonium saccharinate (95%active). ONYXIDE™ 3300 is presently commercially available from StepanCompany, Northfield, Ill.—USA.

Preferably the cationic compound is:

wherein R is a linear or branched alkyl chain having from 1 to 30 carbonatoms, more preferably from 10 to 16 atoms.

In the present invention the nature of the anion counterion X⁻ isimportant. Preferred counterions X⁻ are those which have at least onepreferably two or all three, of the following properties:

-   1) can generate a water-insoluble salt form, by water-insoluble we    mean that less than 10% w/v dissolves in deionised water at 20° C.,    preferably less than 1% w/v;-   2) has a MW of less than 300 (preferably less than 200) but greater    than 50 (preferably greater than 75);-   3) the dissociation constant (Kd) of the salt is less than 10⁻³,    preferably less than 10⁻⁶.

A preferred feature is 2) or 2)+3).

Preferably the counterion X⁻ should have all three above properties.Preferred counterions X⁻ of the invention are selected fromsaccharinate, alkyl sulfate and alkyl benzene sulfate, alkyl, sulfonate,alkyl benzene sulfonate and fatty acid.

The level of cationic compound used depends upon the product type,whether it is a ready to use product or a dilutable formula. Suitablelevels for a ready to use product is 0.001% to 5% w/v, a preferred rangeis 0.01 to 0.5% w/v. A dilutable product requires more active and asuitable range is from 0.01 to 40% w/v, preferably between 0.5 to 20%depending on the dilution ratio.

It has been surprisingly found that the cationic compound, as definedherein, is compatible with anionic surfactants as well as in generalwith anionic polymer based products. The compositions containing thecationic compound, anionic surfactant, non ionic surfactants, polymers,solvents, chelating agents, and other minor actives as dyes,antifoaming, perfumes, preservatives, . . . etc, have cleaningperformance, low fabric damage, and good prevention of soilre-deposition. It has been found surprisingly that the cationic compoundis very effective bactericide even in combination with anionicsurfactants.

The cationic compound described in the compositions of this inventioncan achieve a log5 bacteria reduction at concentrations below 5000 ppmin the final liquid cleaning product, preferably below 1500 ppm. Thecationic compounds described in this invention can also be mixed withlow quantity of other bactericide compounds in order to increase thebactericidal efficacy without any negative effect in terms of cleaningperformance. Examples of these bactericides actives are those previouslydescribed as essential oils (tea tree oil, citronella oil and thymeoil), phenols, alcohols, halogens, aldehydes and acids. The level ofaddition is in this case very low, between 0.001 to 1% w/v, preferablybetween 0.01 to 0.5% w/v.

Examples of surfactants considered in this invention are either anionicsurfactant, non-ionic surfactant and super wetting agents. Preferredlevels of surfactant are from 0.01 to 40% w/v, ideally from 0.1 to 10%w/v and preferably 0.5 to 5% w/v. The non-ionic surfactant is preferablyis an amount of 0.01 to 30% w/v, ideally, 0.1 to 15% w/v or 0.5 to 10%w/v. The nonionic surfactant preferably has a formula RO(CH2CH2O)_(n)Hwherein R is a mixture of linear, even carbon-number hydrocarbon chainsranging from C12H25 to C16H33 and n represents the number of repeatingunits and is a number of from about 1 to about 12. Examples of othernon-ionic surfactants include higher aliphatic primary alcoholscontaining about twelve to about 16 carbon atoms which are condensedwith about three to thirteen moles of ethylene oxide.

Other examples of non-ionic surfactants include primary alcoholethoxylates (available under the Neodol tradename from Shell Co.), suchas C11 alkanol condensed with 9 moles of ethylene oxide (Neodol 1-9),C12-13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5),C12-13 alkanol with 9 moles of ethylene oxide (Neodol 23-9), C12-15alkanol condensed with 7 or 3 moles ethylene oxide (Neodol 25-7 orNeodol 25-3), C14-15 alkanol condensed with 13 moles ethylene oxide(Neodol 45-13), C9-11 linear ethoxylated alcohol, averaging 2.5 moles ofethylene oxide per mole of alcohol (Neodol 91-2.5), and the like.

Other examples of non-ionic surfactants suitable for use in the presentinvention include ethylene oxide condensate products of secondaryaliphatic alcohols containing 11 to 18 carbon atoms in a straight orbranched chain configuration condensed with 5 to 30 moles of ethyleneoxide. Examples of commercially available non-ionic detergents of theforegoing type are C11-15 secondary alkanol condensed with either 9moles of ethylene oxide (Tergitol 15-S-9) or 12 moles of ethylene oxide(Tergitol 15-S-12) marketed by Union Carbide, a subsidiary of DowChemical.

Octylphenoxy polyethoxyethanol type non-ionic surfactants, for example,Triton X-100, as well as amine oxides can also be used as a non-ionicsurfactant in the present invention.

Other examples of linear primary alcohol ethoxylates are available underthe Tomadol tradename such as, for example, Tomadol 1-7, a C11 linearprimary alcohol ethoxylate with 7 moles EO; Tomadol 25-7, a C12-C15linear primary alcohol ethoxylate with 7 moles EO; Tomadol 45-7, aC14-C15 linear primary alcohol ethoxylate with 7 moles EO; and Tomadol91-6, a C9-C11 linear alcohol ethoxylate with 6 moles EO.

A preferred surfactant is an anionic surfactant. Such anionic surfaceactive agents are frequently provided in a salt form, such as alkalimetal salts, ammonium salts, amine salts, amino alcohol salts ormagnesium salts. Contemplated as useful are one or more sulfate orsulfonate compounds including: alkyl sulfates, alkyl ether sulfates,alkylamidoether sulfates, alkyl benzene sulfates, alkyl benzenesulfonates, alkylaryl polyether sulfates, monoglyceride sulfates,alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates,olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkylether sulfosuccinates, alkylamide sulfosuccinates, alkylsulfosuccinamate, alkyl sulfoacetates, alkyl carboxylates, alkylphosphates, alkyl ether phosphates, acyl sarconsinates, acylisethionates, and N-acyl taurates. Generally, the alkyl or acyl radicalin these various compounds comprise a carbon chain containing 12 to 20carbon atoms.

Preferred surfactants are also alkyl naphthalene sulfonate anionicsurfactants of the formula:

wherein R is a straight chain or branched alkyl chain having from about1 to about 25 carbon atoms, saturated or unsaturated, and the longestlinear portion of the alkyl chain is 15 carbon atoms or less on theaverage, M is a cation which makes the compound water soluble especiallyan alkali metal such as sodium or magnesium, ammonium or substitutedammonium cation.

Particularly preferred are alkyl sarcosinate, sulfosuccinate and alkylsulfate anionic surfactants of the formula

wherein R is a straight chain or branched alkyl chain having from about8 to about 18 carbon atoms, saturated or unsaturated, and the longestlinear portion of the alkyl chain is 15 carbon atoms or less on theaverage, M is a cation which makes the compound water soluble especiallyan alkali metal such as sodium or magnesium, ammonium or substitutedammonium cation, and x is from 0 to about 4. Most preferred are thenon-ethoxylated C12-15 primary and secondary alkyl sulfates, especiallysodium lauryl sulfate.

Most desirably, the anionic surfactant according to constituent isselected to be of a type that dries to a friable powder. Thisfacilitates their removal from carpets and carpet fibres, such as bybrushing or vacuuming.

Super wetting agents are used between 0.001 to 10% w/v, preferably from0.01 to 10% w/v, ideally from 0.1 to 5% w/v. The super wetting agents ofthis invention are silicone glycol copolymers and flurosurfactants.

The silicone glycol copolymers are described by the following formula:

Where x, y, m and n are whole number ranging from 0 to 25. X ispreferred between 0-10 and y, m and n between 0-5. R and R′ are straightchain or branched alkyl chain having from about 1 to about 25 carbonatoms, saturated or unsaturated, and the longest linear portion of thealkyl chain is 15 carbon atoms or less on the average. The fluorinatedsurfactant is described in the following formulae:F(CF₂)_(n)—CH₂CH₂—S—CH₂CH₂—COOMF(CF₂)_(n)—N(CH3)(CH2)3-(CH₂CH₂O)_(x)OSO₂MCF₃(CF₂CF₂)_(n)(CFCF)_(m)—(CH₂CH₂O)_(x)—OPO₃M₂

Wherein n, m and x are integers having a value from 0 to 15; preferredvalues are between 1 and 12. M is a cation which makes the compoundwater-soluble especially an alkali metal such as sodium or magnesium,ammonium or substituted ammonium cation.

The super wetting agents described are able to low the surface tensionin water at values below 25 mN/m, in the range between 18 and 25 mN/m atworking condition concentrations of 0.0001 to 1% w/v, preferably between0.001 to 0.1% w/v.

The composition of the present invention may also contain one or morehydrotropes. Examples of suitable hydrotropes are sodium cumenesulfonate (ELTESOL SC40 available from Albright & Wilson), sodium xylenesulfonate (ELTESOL SX40 available from Albright & Wilson), di-sodiummono- and di-alkyl disulfonate diphenyloxide (DOWFAX 3B2 available fromDow Chemicals), n-octane sodium sulfonate (BIOTERGE PAS 7 S or 8 Savailable from Stepan). Levels of hydrotope added are from 0.01% to 15%w/v.

Organic solvents may be added and may be beneficial in term of improvingthe solubility of the cationic compounds in water. The organic solventsshould be water-miscible. Preferably the organic solvent is found atlevels of 0.001 to 15% w/v ideally 0.01 to 15% w/v or 0.5 to 5% w/v. Theorganic solvent constituent of the inventive compositions include one ormore alcohols, glycols, acetates, ether acetates and glycol ethers.Exemplary alcohols useful in the compositions of the invention includeC2-C8 primary and secondary alcohols which may be straight chained orbranched. Exemplary alcohols include pentanol and hexanol. Exemplaryglycol ethers include those glycol ethers having the general structureRa—O—Rb—OH, wherein Ra is an alkoxy of 1 to 20 carbon atoms, or aryloxyof at least 6 carbon atoms, and Rb is an ether condensate of propyleneglycol and/or ethylene glycol having from 1 to 10 glycol monomer units.Preferred are glycol ethers having 1 to 5 glycol monomer units.

By way of further non-limiting example specific organic constituentsinclude propylene glycol methyl ether, dipropylene glycol methyl ether,tripropylene glycol methyl ether, propylene glycol n-propyl ether,ethylene glycol n-butyl ether, diethylene glycol n-butyl ether,diethylene glycol methyl ether, propylene glycol, ethylene glycol,isopropanol, ethanol, methanol, diethylene glycol monoethyl etheracetate and particularly useful is, propylene glycol phenyl ether,ethylene glycol hexyl ether, diethylene glycol hexyl ether.

The chelating agent is added at a level between 0.01 to 5% w/v,preferably between 0.1 to 1% w/v. Examples of chelating agents aredescribed below:

-   -   the parent acids of the monomeric or oligomeric polycarboxylate        chelating agents or mixtures therefore with their salts, e.g.        citric acid or citrate/citric acid mixtures are also        contemplated as useful builder components.    -   borate builders, as well as builders containing borate-forming        materials than can produce borate under detergent storage or        wash conditions can also be.    -   iminosuccinic acid metal salts    -   polyaspartic acid metal salts.    -   examples of bicarbonate and carbonate builders are the alkaline        earth and the alkali metal carbonates, including sodium        carbonate and sesqui-carbonate and mixtures thereof. Other        examples of carbonate type builders are the metal carboxy        glycine and metal glycine carbonate.    -   ethylene diamino tetra acetic acid and salt forms.    -   water-soluble phosphonate and phosphate builders are useful for        this invention.

Examples of phosphate builders are the alkali metal tripolyphosphates,sodium potassium and ammonium pyrophosphate, sodium and potassium andammonium pyrophosphate, sodium and potassium orthophosphate sodiumpolymeta/phosphate in which the degree of polymerisation ranges from 6to 21, and salts of phytic acid. Specific examples of water-solublephosphate builders are the alkali metal tripolyphosphates, sodiumpotassium and ammonium pyrophosphate, sodium and potassium and ammoniumpyrophosphate, sodium and potassium orthophosphate, sodiumpolymeta/phosphate in which the degree of polymerisation ranges from 6to 21, and salts of phytic acid.

The polymers used in this invention at a level between 0.01 to 30% w/v,preferably between 0.1 to 5% w/v. Examples of polymers are:water-soluble compounds include the water soluble monomericpolycarboxylates, or their acid forms, homo or copolymericpolycarboxylic acids or their salts in which the polycarboxylic acidcomprises at least two caroxylic radicals separated from each other bynot more than two carbon atoms, carbonates, bicarbonates, borates,phosphates, and mixtures of any of thereof. The carboxylate orpolycarboxylate builder can be monomeric or oligomeric in type althoughmonomeric polycarboxylates are generally preferred for reasons of costand performance. Suitable carboxylates containing one carboxy groupinclude the water soluble salts of lactic acid, glycolic acid and etherderivatives thereof. Polycarboxylates containing two carboxy groupsinclude the water-soluble salts of succinic acid, malonic acid,(ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaricacid, tartronic acid and fumaric acid, as well as the ether carboxylatesand the sulfinyl carboxylates. Polycarboxylates containing three carboxygroups include, in particular, water-soluble citrates, aconitrates andcitraconates as well as succinate derivates such as thecarboxymethloxysuccinates described in GB-A-1,379,241, lactoxysuccinatesdescribed in GB-A-1,389,732, and aminosuccinates described inNL-A-7205873, and the oxypolycarboxylate materials such as2-oxa-1,1,3-propane tricarboxylates described in GB-A-1,387,447.

Polycarboxylate containing four carboxy groups include oxydisuccinatesdisclosed in GB-A-1,261,829, 1,1,2,2-ethane tetracarboxylates,1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarobyxlates.Polycarboxylates contining sulfo substituents include the sulfosuccinatederivatives disclosed in GB-A-1,398,421, GB-A-1,398,422 and U.S. Pat.No. 3,936,448, and the sulfonated pyrolsed citrates described inGB-A-1,439,000.

Alicylic and heterocyclic polycarboxylates includecyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienidepentacarboxylates, 2,3,4,5,6-hexane—hexacarboxylates and carboxymethylderivates of polyhydric alcohols such as sorbitol, mannitol and xylitol.Aromatic polycarboxylates include mellitic acid, pyromellitic acid andthe phthalic acid derivatives disclosed in GB-A-1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylatescontaining up to three carboxy groups per molecule, more particularlycitrates.

More preferred polymers are homo-polymers, copolymers and multiplepolymers of acrylic, fluorinated acrylic, sulfonated styrene, maleicanhydride, metacrylic, iso-butylene, styrene and ester monomers.

Examples of these polymers are Acusol supplied from Rohm & Haas, Syntransupplied from Interpolymer and Versa and Alcosperse series supplied fromAlco Chemical, a National Starch & Chemical Company.

Antifoaming agents are critical for machine shampoo products: they areused in this invention at a level between 0.01 to 5% w/v. The foam levelin fact doesn't allow to properly use the carpet cleaning machines if itis too high and in any case tends to reduce the mechanical action of thecarpet cleaner machine brushes, having an impact on soil removal.Atifoaming agents are so considered important actives of this invention.

Examples are polydimethylsiloxanes in combination with hydrophobicsilica in different ratios.

Water is present in the compositions at levels of up to 98% w/v, ideallyup to 90% w/v.

Up to 10% w/v, ideally 8%, 5%, 4% or 2% w/v of additional minoringredients can be added, selected from one or more of the following;perfumes, dyes, preservatives and antifoaming agents.

Points of advantage found in this invention:

-   -   The cationic compounds of the invention are compatible with        anionic surfactants and other anionic species such as anionic        polymers.    -   The cationic compounds of the invention, even if complexed        provide a bactericidal action similar to uncomplexed cationic        species.    -   The cationic compounds in fabric cleaning compositions don't        cause any reduction in terms of cleaning performance, fabric        damage and anti-re-deposition.    -   The cationic compounds can be combined with small amount of        other bactericidal actives, such as essential oils, phenols,        alcohols and acids, improving the bactericidal effect without        lowering cleaning performance.

These cationic compounds can be used in liquid and powder carpetcleaning compositions. Examples of liquid compositions are ready to useproducts as triggers and dilutable products as manual and machineshampoos.

These cationic complexes are not very soluble in water, but this pointcan be easily overcome by combining them with anionic and non-ionicsurfactants, by using solvents, hydrotropes and polymers. Heating theliquid compositions up to 60-80° C. can also help to improve thedissolution during manufacture.

A further feature of the invention is the use of a bactericidally activewater-soluble cationic compound in its salt form, wherein the counterionanion has at least one of the following properties:

-   -   1) can generate a water-insoluble salt form, by water-insoluble        we mean that less than 10% w/v dissolves in deionised water at        20° C., preferably less than 1% w/v;    -   2) has a MW of less than 300, preferably less than 200 but        greater than 50, preferably greater than 75°;    -   3) the dissociation constant (Kd) of the salt is less than 10⁻³,        preferably less than 10⁻⁶;        as a bactericidally active component of a fabric treatment        composition comprising from 0.001 to 40% w/v of an anionic        surfactant.        Tests

Several tests have been considered in this invention to evaluate thecompatibility of the cationic complexes in anionic carpet cleaningcompositions (Storage stability test), the bactericidal efficacy of thecationic complexes (AOAC Germicidal and Detergent Sanitizing Action ofDisinfectants method), the cleaning performances (Stain removal test),the anti re-deposition and the carpet damage.

The cleaning performances have been compared with Resolve spot & staincarpet cleaner trigger and with Resolve pet stain & odour carpet cleanertrigger.

Storage Stability Test:

The 100 ml of the liquid compositions were put in to glass jars at 5, 25and 40° C. The formula appearance and pH variation are considered and arating assigned. The storage situation is monitored after 1 month and 3months and compared with the starting values. The data table with thecorresponding storage rating is reported below: Storage rating (SR) pHvariation Liquid appearance 0 0 No difference from reference 1 Less than0.25 No difference from reference 2 From 0.25 to 0.50 No difference fromreference 3 From 0.5 to 1 No difference from reference 4 More than 1 Nodifference from reference 5 From 0.25 to 0.50 Separation and/or colourchange 6 From 0.25 to 0.5 Separation and/or colour change 7 From 0.5 to1 Separation and/or colour change 8 More than 1 Separation and/or colourchange

The higher the rating number, the worse the storage performance. Theanionic species found compatible with the cationic complexes are alsoreported.

Bactericidal Efficacy Test:

The AOAC Germicidal and Detergent Sanitizing Action of Disinfectantsmethod has been used for bactericidal efficacy evaluation.

The efficacy has been tested against Staphylococcus aureus (ATCC 6538)and Enterbacter aerogenes (ATCC13048) and it is expressed as percentagebacteria reduction.

Stain Removal Test:

This method has been designed for the evaluation of stain removalperformance of carpet cleaner compositions and especially of triggerproducts. The Resolve™ spot % stain carpet cleaner trigger and Resolve™pet stain & odour carpet cleaner trigger has been used as a referencefor spot removal products.

The stains were applied to nylon carpets following the procedures below:

-   -   Dirty Motor Oil        -   0.1 grams sprayed with an airbrush using a 5 cm diameter            template. Allow any sediment to settle and decant oil into a            clean container.    -   Ink        -   0.1 grams sprayed with an airbrush using a 5 cm diameter            template—Blue oily ink (Pelikan).    -   Grape juice        -   1.5 gram sprayed with an airbrush using a 5 cm diameter            template—Welch's    -   Mud        -   1.1 grams diluted 1:4 with water, well mixed and applied            with a spatula into a loom with 3 cm diameter—green mud            argital.        -   5 cm diameter template—7 Lipton yellow teabags are put in            200 grams boiling water.    -   Coffee        -   1 gram sprayed with an airbrush using a 5 cm diameter            template—milk (3 ml) & sugar (20 g)    -   Spaghetti sauce        -   0.75 grams applied with a spatula into a loom with 3 cm            diameter—Ragù traditional.

The stains were allowed to set for 24 hours before cleaning. Thecleaning process was carried out by spraying 4 grams of the product ontothe stain, leaving it for 3 minutes and doing 10 strokes in the verticaland then in the horizontal direction using a clean cloth. The area isthen blotted twice and left to dry for 24 hours.

A panel test has been done on stained and cleaned carpet swatches tocheck the stain removal from carpet pile. The panellists are providedwith a new carpet as a 1 reference and a stained carpet as a referenceof 5. The panellists assigned a value to the cleaned carpet swatchesbetween 1 and 5. The lower the rating number, the better the cleaningperformance. The rating number obtained from carpet pile and backing perstain/product is averaged.

Carpet Damage Test:

Multiple (×3) cleaning process steps were done on a blue nylon carpetand red wool carpet to check for any potential damage of thecompositions of this invention to the carpet fibre or colour. Resolve™trigger spot & stain carpet cleaner was used as a reference product.

A panel test is used for evaluating carpet damage. Panellists are givena non-cleaned carpet swatch as a control of 0 per each carpettype/colour. The evaluation scale ranges from 0 to 4, 0 is no colourchange, 4 corresponds to very high colour change.

The responses of the panellist are averaged. Damage rating (DR) Carpetdamage description 0 No colour change or fibre damage 1 Slight colourchange and fibre damage 2 Perceptible colour change and fibre damage 3Evident colour change and fibre damage 4 Strong colour change and fibredamageAn accepted carpet damage rating is parity or below 1.Anti Re-Deposition Test:

This method has been designed for the evaluation of anti re-depositionproduct evaluation.

The soil used has the following composition: Soil components: % byweight Peat Moss 47.7 Cement 21.4 Kaolin clay 8.0 Silica 8.0 Red Ironoxide 1.3 Charcoal 12.6 Mineral oil 1.0A nylon carpet is used for the test.

A cleaning process is carried out by spraying 4 grams of the productonto the carpet, leaving it for 3 minutes and doing 10 strokes in thevertical and then in the horizontal direction using a clean cloth. Thearea is then blotted twice and left to dry for 24 hours.

The carpet is soiled with 5 grams of standard soil. The soil is applied1 gram once by strainer. The soiled carpet is then put with 4 kg ofsteel beads in the jar mill and stirred for 30 minutes at 56 rpm.

Carpet swatches are placed in a dark room temperature chamber (25°C./50% RH) for 24 hours while they dry.

The carpet swatches are the vacuumed doing 3 strokes in the vertical andthen in the horizontal direction.

The water is used as a ‘product’ reference for having no positive ornegative impact on anti re-deposition.

The anti re-deposition performance is evaluated by measuring the carpetwith a portable spectrophotometer before cleaning after soiling andvacuuming. The result is reported as anti re-deposition percentage,where a positive value indicates an anti re-deposition effect and anegative value indicates a product stickness.

EXAMPLES

The liquid compositions are typically prepared by mixing each ingredienttogether in a suitable container.

Examples of compositions forming a part of the present invention relatedto ready to use products are set below in Tab 1 and 2, examples fordilutable machine carpet cleaner liquids are reported in table 3 andexamples for dilutable manual shampoo liquids with are described intable 4. All the various components are identified in Tab 5. TABLE 1 Ex1 Ex 2 Ex 3 Ex 4 Ex 5 Components % % % % % Trilon B 11.20 11.20 11.201.00 1.00 Trilon BS acid 2.00 1.40 2.00 Citric acid 0.11 0.08 StepanolWAC 3.00 3.00 3.00 3.00 3.00 Syntran 1575 3.00 3.00 3.00 Zelan 338 0.150.15 Genapol 26-L-5 0.50 0.50 0.50 Zonyl 7950 0.15 0.15 Onyxide 3300 33%0.50 0.30 0.30 0.35 0.35 Kathon CG/ICP 0.10 0.10 0.10 0.05 0.05 ThymolKristal 0.09 0.09 0.09 0.09 0.09 powder Dowanol PPH 1.50 1.50 1.50 1.50Isopropyl alcohol 2.00 2.00 Soft water 79.61 78.91 78.31 91.65 91.68 pH6.7 8.0 6.5 6.5 8.0

TABLE 2 Ex 6 Ex 7 Ex 8 Ex 9 Ex 10 Components % % % % % Trilon B 1.001.00 1.00 1.00 1.00 Citric acid 0.08 0.08 0.08 0.08 0.08 Stepanol WAC3.00 3.00 3.00 3.00 3.00 Zelan 338 0.15 0.15 0.15 0.15 0.15 Zonyl 79500.15 0.15 0.15 0.15 0.15 Onyxide 3300 33% 0.20 0.50 0.20 0.35 0.50Kathon CG/ICP 0.05 0.05 0.05 0.05 0.05 Thymol Kristal 0.09 0.09 powderFragrance 0.15 0.15 0.15 Dowanol PPH 1.50 1.50 1.50 1.50 1.50 Isopropylalcohol 2.00 2.00 2.00 2.00 2.00 Soft water 91.78 91.48 91.72 91.5791.42 pH 7.8 7.8 7.7 7.7 7.7

TABLE 3 Ex 11 Ex 12 Ex 13 Components % % % Trilon B 8.11 8.11 8.11Trilon BS acid 0.77 0.77 0.77 Sodium bicarbonate 0.06 0.06 0.06 Petro 11liquid 1.23 1.23 1.23 Eltesol SC40 7.00 6.00 9.50 Genapol 26-L-60 2.032.03 2.03 Syntran 1580 1.59 1.59 1.59 Onyxide 3300 1.90 1.90 1.90Silicone antifoam 0.05 0.05 0.05 Fragrance 0.40 0.40 0.40 Dowanol PPH1.00 Dowanol DPnP 1.90 2.85 Soft water 74.96 75.01 73.362 pH 8.7 8.9 8.7

TABLE 4 Ex 14 Ex 15 Components % % Dequest 2066 2.00 2.00 Empicol 033519.00 19.00 Syntran DX 302-1 12.50 12.50 Onyxide 3300 33% 1.40 2.80Fragrance 0.25 0.25 Dye 0.0004 0.0004 Soft water 64.85 63.45 pH 6.9 6.9

TABLE 5 Component Description of component Trilon B EDTA tetrasodiumsalt 40% from BASF Trilon BS acid EDTA acid powder from BASF Citric acidCitric acid from various suppliers Sodium bicarbonate Sodium bicarbonatefrom various suppliers Syntran 1575 Fluorinated acrylic copolymer fromInterpolymer Corporation Syntran 1580 Acrylic copolymer fromInterpolymer Corporation Syntran DX302-1 Acrylic copolymer fromInterpolymer Corporation Onyxide 3300 33% Miristalkonium saccharinate inalcohol from Stepan Onyxide 3300 Miristalkonium saccharinate from StepanStepanol WAC Sodium lauryl sulfate from Stepan Empicol 0335 Sodium alkylsulfate from Hutsman Petro 11 liquid Sodium alkyl naphthalene sulfonatefrom Akzo Eltesol SC40 Sodium cumene sulfonate from Hutsman Genapol26-L-5 Primary alcohol ethoxylate from Hoechst Celanese Genapol 26-L-60Primary alcohol ethoxylate from Hoechst Celanese Kathon CG/ICPIsothiazolinone from Rohm & Haas Thymol Krist powder Thymol from H.Reimer Zonyl 7950 Fluorosurfactant from Dupont Zelan 338 Polycarboxylatefrom Dupont Dowanol PPH 1-phenoxy 2-propanol from Dow chem Dowanol DPnPDipropylene glycol n-propyl ether from Dow chem Isopropyl alcoholIsopropyl alcohol Fragrance Proprietary fragrance from various suppliersExample Results:

The stain removal and carpet damage performances have been compared withResolve spot & stain carpet cleaner trigger and with Resolve pet stain &odour carpet cleaner trigger, considered as two of the market leaders inUS for stain removal products.

Results for Storage Stability Test:

In the table below are reported the storage rating values (SR) per eachstorage condition and the compatibility between onyxide 3300 and anionicspecies. Stability test rating (ready to use product) 1 month 3 monthsOnyxide 3300 is SR SR SR SR SR SR compatible with the Product 5° C. 25°C. 40° C. 5° C. 25° C. 40° C. following anionics species: Ex 1 2 1 1 2 11 Stepanol WAC, Syntran 1575 Ex 2 1 1 1 1 1 1 Stepanol WAC, Syntran 1575Ex 3 0 1 1 1 1 3 Stepanol WAC, Syntran 1575 Ex 4 1 1 1 1 1 1 StepanolWAC, Zelan 338, Zonyl 7950 Ex 5 0 1 1 1 1 5 Stepanol WAC, Zelan 338,Zonyl 7950 Ex 6 0 0 1 0 0 1 Stepanol WAC, Zelan 338, Zonyl 7950 Ex 7 0 02 5 2 6 Stepanol WAC, Zelan 338, Zonyl 7950 Ex 8 0 0 0 0 2 2 StepanolWAC, Zelan 338, Zonyl 7950 Ex 9 0 0 0 0 0 2 Stepanol WAC, Zelan 338,Zonyl 7950 Ex 10 0 0 0 0 0 2 Stepanol WAC, Zelan 338, Zonyl 7950

Stability test rating (dilutable product-manual and machine shampoos) 2weeks Onyxide 3300 is SR SR SR compatible with the Product 5° C. 25° C.40° C. following anionics species: Ex 13 0 0 0 Eltesol SC40, Petro 11,Syntran 1580 Ex 14 0 0 0 Empicol 0335, Syntran DX 302-1 Ex 15 0 0 0Empicol 0335, Syntran DX 302-1

Results for Bactericidal Efficacy Test (Ready to Use Product):Disinfectant efficacy Staphylococcus aureus Enterobacter aerogenes(bacteria reduction % with different contact times) 30 sec 1 min 5 min30 sec 1 min 5 min Reference: 78.677 87.721 98.920 47.500 74.000 99.775Resolve spot & Ex 5 99.442 99.943 99.999 99.999 99.999 99.999 Ex 699.324 99.913 99.999 99.999 99.999 99.999 Ex 7 99.331 99.924 99.99999.999 99.999 99.999 Ex 8 90.000 96.250 99.928 99.999 99.999 99.999 Ex 989.118 96.986 99.952 99.999 99.999 99.999 Ex 10 91.618 97.059 99.93799.999 99.999 99.999Results for Stain Removal Tests (Ready to Use Products):

It has been used Resolve™ Spot and stain trigger and pet stain & odourtrigger products as a references. 3 replicates has been considered pereach product and the values reported in the table below are averaged.Stain removal rating Grape Spaghetti Mud DMO juice Coffee sauce InkResolve ™ Spot and 3.7 3.3 3.0 3.1 3.2 4.2 stain trigger Resolve ™ petstain & 4.0 3.0 3.2 3.0 3.7 4.0 odour trigger Ex 1 4.2 3.2 2.7 3.2 4.03.9 Ex 2 4.2 2.7 3.1 3.7 3.4 3.8 Ex 3 4.3 2.7 3.2 3.7 3.0 3.9 Ex 4 3.83.5 3.1 3.6 3.4 4.2 Ex 5 3.4 3.0 3.2 3.6 3.1 3.8Results for Carpet Damage Test and Anti Re-Deposition (Ready to UseProduct):

It has been used again Resolve™ Spot and stain trigger and pet stain &odour trigger products as references. Per each product/carpet type hasbeen considered 3 replicates and the values reported in the table beloware averaged. Damage test Anti re- Beige Red Green deposition wool woolBlue nylon polyester test Product rating rating rating rating %Resolve ™ Spot and 0.7 0.6 0.1 0.1 10.3 stain trigger Ex 4 0.6 0.6 0.50.0 8.0 Ex 5 1.0 0.8 0.2 0.0 2.5

1. A detergent comprising: a) 0.001% to 40% w/v of a bactericidallyactive water-insoluble cationic compound in its salt form wherein thecounterion anion has at least one of the following properties: 1) cangenerate a water-insoluble salt form wherein less than 10% w/v dissolvesin deionised water at 20° C.; 2) has a MW of less than 300, but greaterthan 50, 3) the dissociation constant (Kd) of the salt form is less than10⁻³; b) 0.001 to 40% w/v of an anionic surfactant; and c) up to 98% w/vof water.
 2. A detergent composition as in claim 1 which additionallycomprises 0.001 to 30% w/v of a non-ionic surfactant.
 3. A detergentcomposition according to claim 1 which additionally comprises 0.001 to10% w/v of a superwetting agent.
 4. A detergent composition according toclaim 3 wherein the super wetting agent is able to lower the surfacetension of water to below 25 mN/m at concentrations of 0.0001 to 1% w/v.5. A detergent composition according to claim 1 which additionallycomprises 0.001% to 15% of a water-miscible organic solvent.
 6. Adetergent composition according to claim 1 which additionally comprises0.01-5% w/v of a chelating agent, 0.01-30% w/v of a polymer and up to 2%w/v of minor ingredients selected from perfumes, dyes, preservatives andantifoaming agents
 7. A detergent composition according to claim 1 whichfurther comprises from 0.001 to 1% w/v of an additional bactericidallyactive product selected from essential oils (tea tree oil, citronellaoil and thyme oil), phenols, alcohols, halogens, aldehydes and acids. 8.A detergent composition according to claim 1 wherein the cationiccompound is

wherein R1, R2, R3 and R4 are independently selected from alkyl, aryl oralkylaryl substituent of from 1 to 26 carbon atoms straight chained orbranched and may include one or more amide, ether or ester linkates, andthe entire cation portion of the molecule has a molecular weight of atleast 165 and X is the counterion anion.
 9. A detergent compositionaccording to claim 8 wherein the cationic compound is

wherein R2 and R3 are each independently the same or different C8-C12alkyl; or R2 is selected from C12-16 alkyl, C8-18 alkylethoxy or C8-18alkylphenoxyethoxy and R3 is benzyl and X is the counterion anion.
 10. Adetergent composition according to claim 7 wherein X⁻ is selected fromsaccharinate, alkyl and alkyl benzene sulfate, sulfonate and fatty acid.11. Use of a bactericidally active water-insoluble cationic compound inits salt form, wherein the counterion anion has at least one of thefollowing properties: 1) can generate a water-insoluble salt formwherein less than 10% w/v dissolves in deionised water at 20° C.; 2) hasa MW of less than 300 but greater than 50; 3) the dissociation constant(Kd) of the salt form is less than 10⁻³; as a bactericidally activecomponent of a fabric treatment composition comprising from 0.001 to 40%w/v of an anionic surfactant.